US8212053B2 - Process for preparing heteroaromatic ring compound having N-Rf group - Google Patents

Process for preparing heteroaromatic ring compound having N-Rf group Download PDF

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US8212053B2
US8212053B2 US12/159,439 US15943906A US8212053B2 US 8212053 B2 US8212053 B2 US 8212053B2 US 15943906 A US15943906 A US 15943906A US 8212053 B2 US8212053 B2 US 8212053B2
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Yuzo Komatsu
Haruhiko Mohri
Hirokazu Aoyama
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Daikin Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C07D473/02—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6
    • C07D473/04—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms
    • C07D473/06—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3
    • C07D473/08—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3 with methyl radicals in positions 1 and 3, e.g. theophylline

Definitions

  • the present invention relates to a process for preparing a heteroaromatic ring compound which is useful as a starting material for a salt of heteroaromatic ring compound usable as an ionic liquid, a curing agent such as an epoxy resin or a polyurethane resin, various agricultural chemicals, intermediates for medicines such as antibiotics and anti-AIDS drugs and intermediates of dye, and further relates to a process for preparing a salt of heteroaromatic ring compound.
  • Liquid salts of imidazole compounds have ionic conductivity, flame retardance, non-volatility, high polarity and solubility, and by making use of these properties, are expected to be ionic liquids having various functions useful for electrolytes for fuel cell, secondary battery, capacitor, dye-sensitized solar cell and electrochromic device, or reaction media, catalyst, and chemical separation and reprocessing of nuclear fuel.
  • JP2003-62467A discloses an ionic liquid composition containing 1-(2,2,2-trifluoroethyl)-3-methylimidazolium trifluoromethanesulfonate.
  • This salt of an imidazole compound is prepared by allowing 1-(methoxyethyl)-3-methylimidazolium trifluoromethanesulfonate to react with trifluoromethanesulfonic anhydride in the presence of trifluoroethanol and pyridine as disclosed in P. Bonhote et al., Inorganic Chemistry, 35, pp. 1168-1178 (1996).
  • a pyrrole compound or an indole compound is allowed to react with fluoroalkene such as CF 2 ⁇ CF 2 , CF 2 ⁇ CFCl or CF 2 ⁇ CFCF 3 in the presence of metallic potassium or metallic sodium, and a pyrrole compound or an indole compound in which a N—H group of the pyrrole compound or the indole compound has been added to the fluoroalkene can be obtained at yield of 60 to 88%.
  • Alkali metals described in these V. V. Rudyuk et al., J. Fluorine Chem., 125, pp. 1465-1471 (2004), D. C. England et al., J. Am. Chem. Soc., 82, pp. 5116-5122 (1960) and U.S. Pat. No. 2,861,990 are substances which are so easily reactable with water, and handling thereof is not easy because water control of all chemicals to be used in the reaction and water control in working environment are necessary. In addition, in these processes, a step for removing alkali metal salt produced after the reaction is required.
  • the present inventors have studied a process for preparing an imidazole compound having a fluorine-containing group at high yield, and as a result, unexpectedly have found that by subjecting an imidazole compound in a molten state to reaction in the absence of a solvent, an imidazole compound having a fluorine-containing group can be prepared at high yield even without forming the imidazole compound into an alkali metal salt or using a catalytic amount of alkali metal.
  • the present inventors have made further investigations based on this finding, and have completed the present invention.
  • the present invention relates to a process (the first preparation process) for preparing a compound (C) comprising a heteroaromatic ring structure having a N—Rf group in its ring, which is characterized in that a heteroaromatic ring compound (A) having a N—H group in its ring is allowed to react, in the absence of alkali metal, with a fluoroalkene (B) represented by the formula (B):
  • R b1 , R b2 and R b3 are the same or different and each is H, halogen atom, a functional group or a monovalent organic group which may be substituted by halogen atom, may have an ether bond and may have a polymerizable group, and
  • R c1 is the same as R b1 of the formula (B);
  • R c2 is the same as R b2 of the formula (B);
  • R c3 is the same as R b3 of the formula (B).
  • the present invention relates to a process (the second preparation process) for preparing a salt (E) comprising a heteroaromatic ring structure having a N—Rf group in its ring, which is characterized in that subsequently to the above-mentioned preparation process, a salt forming compound (D) is acted on the obtained compound (C) comprising a heteroaromatic ring structure having a N—Rf group in its ring and if necessary, anion exchanging is further carried out.
  • the present invention further relates to a novel compound (C1) comprising a heteroaromatic ring structure having a N—Rf group in its ring and a novel salt (E1) comprising a heteroaromatic ring structure having a N—Rf group in its ring.
  • the first preparation process of the present invention is a process for preparing the compound (C) comprising a heteroaromatic ring structure having a N—Rf group in its ring, which is characterized in that the heteroaromatic ring compound (A) having a N—H group in its ring is allowed to react, in the absence of alkali metal, with the fluoroalkene (B) represented by the above-mentioned formula (B).
  • heteroaromatic ring compound (A) having a N—H group in its ring which is a starting material examples of the heteroaromatic ring compounds (A1) represented by the formula (A1):
  • a compound having an imidazole skeleton, a pyrrole skeleton, a pyrazole skeleton, a triazole skeleton, an indole skeleton, a purine skeleton or a purine derivative is preferable from the viewpoint of easy synthesis and availability.
  • heteroaromatic ring compound (A1) represented by the above-mentioned formula (A1) are an imidazole compound represented by the formula (A1-1):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them, a pyrrole compound represented by the formula (A1-2):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them, a pyrazole compound represented by the formula (A1-3):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them, a triazole compound represented by the formula (A1-4):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them, an indole compound represented by the formula (A1-5):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them, a purine compound represented by the formula (A1-6):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them, and a purine derivative represented by the formula (A1-7):
  • R a is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a is present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by R a ;
  • R and R′ are the same or different and each is hydrogen atom, an alkyl group, an arylalkyl group, an organosilicon group, an alkoxyl group or a carboxyester group;
  • Ys are the same or different and each is ⁇ O, —NRR′, —OR, F or F 2 , and compounds explained infra.
  • R a examples are, for instance, groups raised below.
  • fluorine atom and chlorine atom are preferably fluorine atom and chlorine atom, especially fluorine atom.
  • Examples are carboxyl group (—COOH), carboxylic acid ester group (—COOR), nitrile group (—CN), amino group (—NH 2 ), alkylamino group (—NR 2 , —NHR), carboxamide group (—CONR 2 , —CONHR), alkyl ether group (—OR), silyl ether group (—OSiR 3 ), thiol group (—SH), thioether group (—SR) and nitro group, preferably carboxylic acid ester group, nitrile group, amino group, alkylamino group, carboxamide group, alkyl ether group, silyl ether group, thiol group and thioether group.
  • carboxyl group (—COOH), carboxylic acid ester group (—COOR), nitrile group (—CN), amino group (—NH 2 ), alkylamino group (—NR 2 , —NHR), carboxamide group (—CONR 2 , —CONHR), alkyl ether group (—OR), silyl ether group (—OSiR 3 ), thiol group (—SH), thioether group (—SR) and nitro group are allowable as a substituent group to be bonded to the benzene ring (Rs are the same or different, and are preferably monovalent hydrocarbon groups).
  • Examples of the imidazole compounds of the formula (A1-1) are, for instance, compounds having R a1 shown in Table 1.
  • Examples of the pyrrole compounds of the formula (A1-2) are, for instance, compounds having R a2 shown in Table 2.
  • Examples of the pyrazole compounds of the formula (A 1-3) are, for instance, compounds having R a3 shown in Table 3.
  • Examples of the triazole compounds of the formula (A1-4) are, for instance, 1,2,4-triazole compounds having R a4 shown in Table 4.
  • Examples of the indole compounds of the formula (A1-5) are, for instance, compounds having R a5 and R a6 shown in Table 5.
  • Examples of the purine compounds of the formula (A1-6) are, for instance, compounds having R a7 and R a8 shown in Table 6.
  • Examples of the purine derivatives of the formula (A1-7) are, for instance, compounds having R a9 shown in Table 7.
  • heteroaromatic ring compounds (A) are, for instance, benzimidazole compounds shown in Table 8, 1,2,3-triazole compounds shown in Table 9, tetrazole compounds shown in Table 10, isoindole compounds shown in Table 11, indazole compounds shown in Table 12 and benzotriazole compounds shown in Table 13.
  • the fluoroalkene (B) which is allowed to react with the heteroaromatic ring compound (A) and is represented by the formula (B):
  • R b1 , R b2 and R b3 are the same or different and each is H, halogen atom, a functional group or a monovalent organic group which may be substituted by halogen atom, may have an ether bond and may have a polymerizable group, is one being capable of undergoing addition reaction with the N—H group of the heteroaromatic ring compound (A).
  • R b1 , R b2 and R b3 especially at least either R b1 or R b2 has the formula (b-1): —(CF 2 ) m1 —
  • m2 is an integer of 1 to 10,000
  • m4 is an integer of 1 to 3,000, and/or
  • R b1 , R b2 and R b3 may be a polymerizable group (b-6).
  • the polymerizable group are, for instance, a carbon-carbon double bond, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, a thiol group and a thioisocyanate group, especially preferably a carbon-carbon double bond.
  • R b1 , R b2 and R b3 are those raised below.
  • carboxyl group —COOH
  • carboxylic acid ester group —COOR
  • CN nitrile group
  • fluoroalkene (B) are, for instance, fluorine-containing olefins such as CF 2 ⁇ CF 2 , CF 2 ⁇ CF(CF 3 ), CF 2 ⁇ C(CF 3 ) 2 , CF 2 ⁇ C(CF 3 )Br, CF 2 ⁇ C(CF 3 )Cl, CF 2 ⁇ C(CF 3 )I, CF 2 ⁇ CFBr, CF 2 ⁇ CFCl, CF 2 ⁇ CFI, (CF 3 ) 2 CFCF 2 CF ⁇ CF 2 , (CF 3 ) 2 CFCF ⁇ CFCF 3 , (CF 3 ) 2 C ⁇ CFCF 2 CF 3 , CF 2 ⁇ CH 2 , CF 2 ⁇ CFH, CF 2 ⁇ CF(Rf B ) n CF ⁇ CH 2 (Rf B is CF 2 CF 2 , CF 2 CFCl, CF 2 CF(CF 3 ) or CF 2 CH 2
  • the heteroaromatic ring compound (A) having a N—H group is allowed to react with the fluoroalkene (B) in the absence of alkali metal.
  • the first preparation process differs from the preparation processes of subjecting a heteroaromatic ring compound to reaction in the form of an alkali metal salt which are disclosed in V. V. Rudyuk et al., J. Fluorine Chem., 125, pp. 1465-1471 (2004), D. C. England et al., J. Am. Chem. Soc., 82, pp. 5116-5122 (1960) and U.S. Pat. No. 2,861,990 because in the present invention, the heteroaromatic ring compound (A) having a N—H group is subjected to reaction, and also differs from the reactions disclosed in V. V. Rudyuk et al., J. Fluorine Chem., 125, pp.
  • a metal which is not allowed to be present in a reaction system is alkali metal, and also presence of other metal being capable of taking part in the reaction directly or as a catalyst is not necessary. Also it is not especially necessary to allow a metal to be present even in the form of a salt or a complex.
  • the reaction may be carried out in a solution of the heteroaromatic ring compound (A) or in a molten state of the heteroaromatic ring compound (A).
  • Examples of a usable reaction solvent are, for instance, diethyl ether, t-butyl methyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, dimethoxymethane, dimethoxyethane, diglyme, triglyme, tetraglyme, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, benzene, toluene, xylene, chloroform, methylene chloride, dichloroethane, trichloroethane, dichloropentafluoropropane, dichlorofluoroethane, trichlorotrifluoroethan
  • the heteroaromatic ring compound preferable are diethyl ether, t-butyl methyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, triglyme, tetraglyme, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, dimethyl sulfoxide and sulfolane.
  • a concentration of the solution may be optionally selected depending on kind of the heteroaromatic ring compound, kind of a solvent, kind of the fluoroalkene and a reaction temperature. As far as a part thereof is homogeneously dissolved, a higher concentration is preferable.
  • the concentration is preferably not less than 30% by mass, further preferably not less than 60% by mass.
  • a reaction pressure is not limited particularly. The reaction proceeds at any pressure as far as the fluoroalkene can contact with the solution containing the heteroaromatic ring compound.
  • the reaction is conducted in the absence of a solvent with the heteroaromatic ring compound (A) being in a molten state, from the viewpoint that no operation for separating a solvent is necessary and production cost is decreased.
  • the molten state of the heteroaromatic ring compound encompasses not only a molten state of the heteroaromatic ring compound alone but also a molten state of the heteroaromatic ring compound alone at a temperature less than its melting point by blending a melting point depressor.
  • Examples of a melting point depressor are the above-mentioned reaction solvents which are used in an amount being capable of dissolving or swelling the heteroaromatic ring compound.
  • the reaction temperature is a melting point of the heteroaromatic ring compound (A) (or a reduced melting point) or more and less than its decomposition temperature.
  • the reaction pressure is not limited particularly. The reaction proceeds at any pressure as far as the fluoroalkene can contact with the molten substance containing the heteroaromatic ring compound.
  • a method of introducing the fluoroalkene (B) to a reaction system is not limited particularly.
  • a method of introducing gasified fluoroalkene under pressure to the solution of the heteroaromatic ring compound (A) or to the heteroaromatic ring compound (A) in a molten state or a method of adding dropwise fluoroalkene to the solution of the heteroaromatic ring compound (A) or to the heteroaromatic ring compound (A) in a molten state.
  • the heteroaromatic ring compound (C) having a N—Rf group in its ring which is obtained in the first preparation process is a compound obtained by adding the fluoroalkene (B) to the N—H group of the heteroaromatic ring compound (A) having a N—H group in its ring.
  • This compound is a fluorine-containing heteroaromatic ring compound represented by the formula (C1):
  • the above-mentioned fluorine-containing heteroaromatic ring compound (C) is a compound obtained by converting the N—H group of the heteroaromatic ring compound (A) to the N—Rf group.
  • a compound having an imidazole skeleton having N—H group in its ring, a compound having a pyrrole skeleton having N—H group in its ring, a compound having a pyrazole skeleton having N—H group in its ring, a compound having a triazole skeleton having N—H group in its ring, a compound having an indole skeleton having N—H group in its ring, a compound having a purine skeleton having N—H group in its ring and a purine derivative having N—H group in its ring are formed into a compound having an imidazole skeleton having N—Rf group in its ring, a compound having a pyrrole skeleton having N—Rf group in its
  • heteroaromatic ring compound (C1) represented by the above-mentioned formula (C1) are a fluorine-containing imidazole compound represented by the formula (C1-1):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf is Rf 1 where Rf 1 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-1), a fluorine-containing pyrrole compound represented by the formula (C1-2):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf is Rf 2 where Rf 2 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-2), a fluorine-containing pyrazole compound represented by the formula (C1-3):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf is Rf 3 where Rf 3 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-3), a fluorine-containing triazole compound represented by the formula (C1-4):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf is Rf 4 where Rf 4 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-4), a fluorine-containing indole compound represented by the formula (C1-5):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them;
  • Rf is Rf 5 where Rf 5 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-5), a fluorine-containing purine compound represented by the formula (C1-6):
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them;
  • Rf is Rf 6 where Rf 6 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-6), and a fluorine-containing purine derivative represented by the formula (C1-7):
  • R a is halogen atom, a functional group or an organic group and may be present or may not be present;
  • Ys are the same or different and each is ⁇ O, —NRR′, —OR, F or F 2 ;
  • R and R′ are the same or different and each is hydrogen atom, an alkyl group, an arylalkyl group, an organosilicon group, an alkoxyl group or a carboxyester group;
  • Rf is Rf 7 where Rf 7 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (C1-7), and examples of the substituent groups thereof are those concretely exemplified in the heteroaromatic ring compound (A1) and the fluoroalkene (B).
  • heteroaromatic ring compound (C) having N—Rf group in its ring examples include fluorine-containing imidazole compounds shown in Table 14, fluorine-containing pyrrole compounds shown in Table 15, fluorine-containing pyrazole compounds shown in Table 16, fluorine-containing triazole compounds shown in Table 17, fluorine-containing indole compounds shown in Table 18, fluorine-containing purine compounds shown in Table 19, fluorine-containing purine derivatives shown in Table 20, fluorine-containing benzimidazole compounds shown in Table 21, fluorine-containing 1,2,3-triazole compounds shown in Table 22, fluorine-containing tetrazole compounds shown in Table 23, fluorine-containing isoindole compounds shown in Table 24, fluorine-containing indazole compounds shown in Table 25, and fluorine-containing benzotriazole compounds shown in Table 26.
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf c1 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c1 group from the formula (C-1); Rf c1 is not —CFHCF 3 , —CF 2 CFZ 1 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl).
  • R a s are the same or different, and each is preferably H, F, Cl, —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9 , —COOR, —CN, -Ph (phenyl group), —CH 2 CN, —CH 2 COOR, —CH 2 SR, —CH 2 CH(NR 2 )COOR, —(CF) n F, —(CF) n H, —CF 2 CF(CF 3 )H or —(CF 2 CH 2 ) n H (Rs are the same or different, and each is a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 10,000).
  • Rf c1 is one represented by the formula (c-1):
  • R c-1a and R c-1b are the same or different, and each is F, —(CF 2 ) q F, —O(CF 2 ) q F, —CF(CF 3 ) 2 , —(OCF 2 CF(CF 3 )) p —O(CF 2 ) q F, —(OCF 2 CF(CF 3 )) p —OCF 2 CF 2 CF ⁇ CH 2 , —(OCF 2 CF(CF 3 )) p —OCF 2 CF 2 CF 2 CH 2 I, —(OCF 2 CF(CF 3 )) p —O(CF 2 ) q CFClCF 2 Cl, —(OCF 2 CF(CF 3 )) p —O(CF 2 ) q CF 2 I, —(CF 2 ) q —(OCF(CF 3 )CF 2 ) p OCF(CF 3 )COOR, —(CF 2 ) q
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf c2 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c2 group from the formula (C-2);
  • Rf c2 is not —CFHCF 3 , —CF 2 CZ 1 Z 2 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl;
  • Z 2 is H, F, Cl, an alkyl group, a fluorinated alkyl group or a chlorinated alkyl group).
  • R a and Rf c2 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf c3 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c3 group from the formula (C-3); Rf c3 is not —CFHCF 3 , —CF 2 CFZ 1 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl).
  • R a and Rf c3 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf c4 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c4 group from the formula (C-4); Rf c4 is not —CFHCF 3 , —CF 2 CFZ 1 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl).
  • R a and Rf c4 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them;
  • Rf c5 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c5 group from the formula (C-5);
  • Rf c5 is not —CFHCF 3 , —CF 2 CZ 1 Z 2 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl;
  • Z 2 is H, F, Cl, an alkyl group, a fluorinated alkyl group or a chlorinated alkyl group).
  • R a and Rf c5 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • R a is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring and/or the aromatic ring are substituted by them;
  • Rf c6 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c6 group from the formula (C-6); Rf c6 is not —CFHCF 3 , —CF 2 CFZ 1 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl).
  • R a and Rf c6 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • R a is halogen atom, a functional group or an organic group and may be present or may not be present;
  • Ys are the same or different and each is ⁇ O, —NRR′, —OR, F or F 2 ;
  • R and R′ are the same or different and each is hydrogen atom, an alkyl group, an arylalkyl group, an organosilicon group, an alkoxyl group or a carboxyester group;
  • Rf c7 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c7 group from the formula (C-7);
  • Rf c7 is not —CFHCF 3 , —CF 2 CFZ 1 H and —CF ⁇ CFZ 1 (Z 1 is F or Cl).
  • R a and Rf c7 are the same as R a and Rf c1 , respectively of the structural formula (C-1).
  • Rf c1 to Rf c7 in the fluoroalkyl group represented by the formula (c) are those having at least one kind of the units represented by the formulas (b-1) to (b-5) as Rb 1 to Rb 3 of the fluoroalkene (B) and/or those having the polymerizable group (b-6) at the end of at least one of R b1 to R b3 .
  • Preferable example of the polymerizable group is a carbon-carbon double bond.
  • heteroaromatic ring compounds (C1) which are novel compounds
  • those having CF 3 group or oxygen atom as the Rf group are preferable as a starting material functioning to lower crystallinity and provide an ionic liquid having a low melting point.
  • Rf groups having two or more CF 3 groups or two or more oxygen atoms are preferable as a starting material functioning to lower crystallinity and provide an ionic liquid having a low melting point.
  • the second preparation process of the present invention is the process for preparing the salt (E) having an heteroaromatic ring structure having a N—Rf group in its ring, which is characterized in that a salt forming compound (D) is acted on the heteroaromatic ring compound (C) having a N—Rf group in its ring and obtained by the above-mentioned first preparation process, and if necessary, anion exchanging is carried out.
  • salt forming compound (D) examples include acids or alkylating agents represented by the formula (D1): Rd—X 1 .
  • inorganic acids such as HF, HCl, HBr, HI, HClO 4 , HNO 3 , H 2 CO 3 , H 2 SO 4 , HBF 4 , HPF 6 , HSbF 6 , HAlCl 4 , HAlF 4 , HAsF 6 and HSO 3 F
  • organic acids such as R—SO 3 H, R—COOH and R—PO 3 H
  • alkylating agents (Rd is an alkyl group) there are compounds having X 1 of F, Cl, Br, I, —OSO 2 R, —OCO 2 R, —OCOR or —OPO 3 R (R is a monovalent hydrocarbon group).
  • Rd are, for instance, hydrogen atom; linear or branched alkyl groups having 1 to 10 carbon atoms such as CH 3 , C 2 H 5 , n-C 3 H 7 , i-C 3 H 7 and C 4 H 9 ; linear or branched fluoroalkyl groups having a unit such as CF 3 , C 2 F 5 , n-C 3 F 7 , i-C 3 F 7 , C 4 F 9 , CF 2 CF 2 Cl, CF 2 CF 2 Br, CF 2 CF 2 I, CH 2 CF 3 , (CF 2 CF 2 ) v H (v is an integer of 1 to 5), CF 2 CHFCF 3 , CF 2 CH 3 , CF 2 CFClH, CF 2 CH(CF 3 ) 2 , CF 3 CH 2 CH 2 , C 2 F 5 CH 2 CH 2 , n-C 3 F 7 CH 2 CH 2 , i-C 3 F 7 CH 2 CH 2 , C 4 F 9
  • an acid is used as the salt forming compound (D)
  • an alkylating agent is used as the salt forming compound (D)
  • the fluorine-containing heteroaromatic ring compound (C) is a compound having an imidazole skeleton, for example, the fluorine-containing imidazole compound (C1-1) or the fluorine-containing benzimidazole compound, the fluorine-containing purine compound (C-6) or the fluorine-containing purine derivative (C-7), the above-mentioned salt forming reaction proceeds especially satisfactorily, and Rd is bonded to nitrogen atom other than N—Rf of the fluorine-containing heteroaromatic ring to give a cation and X 1 becomes a counter anion.
  • the counter anion can be changed to various anions, if necessary, by anion exchange of the counter anion of the salt of fluorine-containing heteroaromatic ring compound obtained by allowing such a salt forming compound (D) to act on the heteroaromatic ring compound.
  • the compound may be a polymer chain containing 1 to 100% by mass of a polymer unit represented by:
  • a copolymerizable comonomer is not limited particularly, and may be optionally selected depending on characteristics intended to be imparted.
  • Nonlimiting examples of preferable comonomers are, for instance, CF 2 ⁇ CF 2 , CF 2 ⁇ CF(CF 3 ), CF 2 ⁇ CFCl, CF 2 ⁇ CH 2 , CF 2 ⁇ CFH, perfluoro(butenyl vinyl ether), perfluoro-2,2-dimethyldioxole, perfluorodioxole, CH 2 ⁇ CH 2 , CH 2 ⁇ CH(CH 3 ), CH 2 ⁇ CHCH ⁇ CH 2 , CH 2 ⁇ CHCl, CH 2 ⁇ CCl 2 , CH 2 ⁇ CHCO 2 R (R is hydrogen atom or an alkyl group which may be substituted by hydrogen atom or halogen atom), CH 2 ⁇ C(CH 3 )CO 2 R (R is hydrogen atom or an alkyl group which may be substituted by hydrogen atom or
  • Examples of the salt (E) of fluorine-containing heteroaromatic ring compound so-obtained by acting the salt forming compound (D) and if necessary, conducting anion exchange are, for instance, a salt of heteroaromatic ring compound represented by the formula (E1):
  • Rf is Rf e where Rf e is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf group from the formula (E1); Rd is H or a monovalent organic group; X is a counter anion.
  • R a s are the same or different, and each is halogen atom, a functional group or an organic group and may be present or may not be present, and when R a s are present, the whole or a part of hydrogen atoms of the heteroaromatic ring are substituted by them;
  • Rf c1 is the same as the formula (c) or is a monovalent organic group which may have at least one residue defined by deleting Rf c1 group from the formula (C-1);
  • Rf c1 is not —CF 2 CF 2 H, —CF ⁇ CF 2 , —CF 2 CFClH, —CF 2 ⁇ CFCl and —CFHCF 3 ;
  • Rd is H or a monovalent organic group;
  • X is a counter anion, is a novel compound.
  • Rf c1 is preferably one having the perfluoroalkylene group of the formula (b-4) having a branched chain and/or the fluoroether unit of the formula (b-5), especially preferably one which has the perfluoroalkylene group of the formula (b-4) having a branched chain and two or more CF 3 groups or two or more oxygen atoms and/or the fluoroether unit of the formula (b-5) since a liquid state is easily exhibited at room temperature.
  • the end of at least one of R a and Rf c1 may be the polymerizable group (b-6).
  • the polymerizable group are, for instance, a carbon-carbon double bond, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, a thiol group and a thioisocyanate group, and especially preferable is a carbon-carbon double bond.
  • the heteroaromatic ring compound (C) having a N—Rf group in its ring which is prepared by the first preparation process of the present invention not only is useful as a starting material for the second preparation process but also can be expected as various materials comprising a heteroaromatic ring compound having a stable N—Rf group in the ring thereof, for example, curing agents such as an epoxy resin and a polyurethane resin, various agricultural chemicals, intermediates for medicines such as antibiotics and anti-AIDS drugs and intermediates of dyes.
  • the salt (E) of heteroaromatic ring compound having a N—Rf group in its ring which is prepared by the second preparation process of the present invention can be used as various materials comprising a heteroaromatic ring compound having a stable N—Rf group in the rings thereof, for example, ionic liquids having various functions useful for electrolytes for fuel cell, secondary battery, capacitor, dye-sensitized solar cell and electrochromic device, and reaction media, catalysis, and chemical separation and reprocessing of nuclear fuel, and in addition, can be expected to be curing agents such as an epoxy resin and a polyurethane resin, various agricultural chemicals, intermediates for medicines such as antibiotics and anti-AIDS drugs and intermediates of dyes.
  • curing agents such as an epoxy resin and a polyurethane resin, various agricultural chemicals, intermediates for medicines such as antibiotics and anti-AIDS drugs and intermediates of dyes.
  • the salt (E) of heteroaromatic ring compound having a N—Rf group in its ring is a solid at normal temperature, as described in the above-mentioned publications, by dispersing or dissolving the salt (E) of heteroaromatic ring compound having a N—Rf group in its ring in a polymer, a solvent or an ionic liquid, ionic conductivity and a function of accelerating dispersion of additives can be exhibited by participation of a structure of N—Rf group.
  • Measuring methods used in the present invention are as follows.
  • the crude reaction product was subjected to refining as it was with a developing solvent of hexane and ethyl acetate of 8:1 by using silica gel chromatography to obtain 56.1 g of a product (yield: 85%).
  • the crude reaction product was subjected to refining as it was with a developing solvent of hexane and ethyl acetate of 3:1 by using silica gel chromatography to obtain 23.6 g of a product (yield based on a diene compound: 71%).
  • THF 1-(1,1,2,2-tetrafluoroethyl)imidazole
  • this polymer was poly[1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium methacrylate] having a polymer side chain converted to imidazolium cation.
  • a N—H group of a heteroaromatic ring compound can be converted directly to a N—Rf group at a high reaction yield without using a catalyst.
  • many kinds of novel fluorine-containing compounds can be easily synthesized, and as a result, a fluorine-containing ionic liquid having a low melting point and characterized by easily compatibilizing a polar compound in a matrix such as a fluorine-containing solvent or a fluorine-containing resin can be obtained.

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